Method of recovery of light hydrocarbons



Aug. 8, 1944. D. G. BRANDT METHOD 0F RECOVERY 0F LIGHT HYDROQARBONS Filed Jan. 22. 1942 ATTORNEY Patented Aug. 8, 1944 METHOD OF RECOVERY OF LIGHT HYDROCARBONS David G. Brandt, Westfield, N. J., assignor to Cities Service Oil Company, New York, N. Y., a corporation of Pennsylvania Application January 22, 1942, Serial No. 427,765

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'I'his invention relates to an improved process for recovering and separating desired volatile hydrocarbons from mixtures thereof with lower and higher boiling 'constituents such as occur in natural gas' and in the pressure distillates of a petroleum cracking operation. This application ls a continuation-impart of and an improvement on the disclosures of applicants pending applications Serial No. 225,079, filed August 16, 1938, and Serial No. 371,929,1i1ed December 27, 1940.

No presently known commercial method for separating desired liqueable hydrocarbons such as Ca hydrocarbons from natural gas or cracking still overhead products is operatable to effect substantially complete separation and recovery of the C3 hydrocarbons. The successive oil absorption and distillation steps whereby C3 hydrocarbons are partially separated by present known methods are not adapted to the problem of effecting high substantially complete recovery of Cs hydrocarbons, primarily because the initial absorption operation is not selective and effects absorption of considerable quantities of undesired C1 and C2 hydrocarbons. The thus absorbed C1 and Cz hydrocarbons interfere with the presently used methods for recovering the absorbed C3 hydrocarbon vapors liberated from the absorption oil by liquefaction and rectification, and any attempt to effect substantially complete recovery of C: hydrocarbons would require excessive reabsorption and rectification operations.

A primary object of the present invention is to provide an elcient and economical process which is adapted for effecting the separation and substantially complete recovery and purification of light hydrocarbons such as C3 and C4 hydrocarbons from mixtures thereof with higher boiling hydrocarbons and with undesired C1 and Cz hydrocarbons.

As pointed out in application Serial No. 371,929, it is practically impossible by present known methods to make a direct fractionation of a mixture of such hydrocarbons and to separate the C1 and C2 from the C3 and higher hydrocarbons at the high pressures and normal water co'ndens- 'ing temperatures which are desirable for the economical handling of such hydrocarbon mixtures. When a hydrocarbon mixture containing Cz and Ca hydrocarbons is-subjected to fractionation under a pressure of the order of 500 pounds per square inch, a considerable amount of Cs hydrocarbons must inevitably be removed overhead with'the C2 hydrocarbons because the C3 hydrocarbons are so near their critical temperature and pressure conditions that practicallyhno heat of vaporization is required to distil them over;

It was further observed in` application Serial No. 371,929 that in effecting preliminary separa- 'tion of the 'undesired C1 4and Cz hydrocarbons from the absorption oilby'rectification, it is necessary to use a reflux containing C3 hydrocarbons, and thereby develop partial pressure effects which insure eicient removal of the undesired hydrocarbons without developing the critical conditions which prevent efcient separation where only Cz hydrocarbon reflux is available. According to the disclosure of that application an efficient high recovery of desired hydrocarbons including Ca hydrocarbons can be obtained while carrying out the preliminary complete separation of C1 and C2 hydrocarbons by selectively reabscrbing C: hydrocarbon vapors removed overhead from such preliminary rectification treatment, under high pressure, and returning the thus reabsorbed C3 hydrocarbons to the rectilication zone.

In accordance with the present invention the preliminary absorption operation is preferably carried out at the gas supply pressure and at a comparatively low temperature to give the heavy gasoline or other absorption oil f ull opportunity `for selective absorption of the desired hydrocarbons and for selective rejection of most of the undesired hydrocarbons. The stabilizing operation on the enriched absorption oil is preferably carried out under a comparatively high pressure not substantially below 500 pounds, and under conditions of temperature and reflux such as to separatey substantially all the undesired hyd-rocarbons from the rich absorber oil.

In successive distillation stages the pressure is gradually dropped while successively separating Ca hydrocarbons in the second stage, C4 hydrocarbons in the third stage, and light gasoline in the nal stage; after which the heavy denuded gasoline residue or absorption oil may be reture to be treated, which may be natural gas or the pressure distillate and gas-mixture from a petroleum cracking operation, andl which may` into the absorber through the line I2 pass upwardly through the absorber in countercurrent contact with an absorption oil which is introduced into the upper part of the absorber throughs. valved connection I8. Absorber Ill is preferably operated under a` pressure and temperature so chosen that propane, propylene and 4 higher molecular .weight hydrocarbons are absorbed and that 'ethane and lower molecular weight gases are discharged from the top of the absorber throughu a line I6 past a pressure-controlled relief valve I4. Absorber I8 is .normally operated under a pressure within the range 10U-400 pounds per square inch, although a higher operating pressure for the absorber may sometimes be used in processing high pressure natural gas. 'The absorption' oil which is introduced into the absorber ID `may comprise any suitable oil adapted to perform the absorption operation. In treating pressure distillate the absorption oil may be a product of the treatment comprising a high boiling point mixture of hydrocarbons obtained as a residue of the I'treatment after stabilization and fractionation of the distillate. Y f

The rich absorption oil which collects at the bottom of the absorber I8 mixes there directly with any liquid hydrocarbon introduced through the line I2, and the resulting mixture is withdrawn through a draw-off and forced by means of a pump 22 at `a high pressure of say 50G-600 pounds 'per quare inch through a preheater 24 and then into a stabilizing column 26, preferably at an .intermediate point thereof. A rectifying operation is carried out within the stabilizer 26 for the rpurpose of distilllng off undesired gaseous hydrocarbons including ethane and ethylene and lower weight molecular constituents from the hydrocarbon mixture, in order to producea stacomprise hydrocarbons boiling in the gasoline some C3 hydrocarbons and even some sobutane or other G4 hydrocarbons This overhead vapor mixture leaves the top of the column 26 through a vapor line 32 and enters the lower end of an absorber 34 which is operated at a pressure substantially the same as the operating pressure of the stabilizer 26. The pressure in the .absorber 34 need only be' slightly lower thane that of the operating pressure of stabilizer 26 to allow for 0 vapor fiow from the top of stabilizer 26 into vabsorber 34.

The absorption oil which is used in absorber 34 may be the same as that supplied to the absorber I0 and thereforemay be introduced into the top of the absorber 34 through a valved extension 36 of line I8; This absorption ollas introduced into .f the absorbers I0 and 34, may be vprecooled to a relatively low temperature.v The rich absorption oil which collects at the bottom of the absorber 34 is removed through a draw-olf line 38 and is introduced into stabilizing column 26 either through feed line 20, or at a point farther up the i column. `If necessary a pump may be provided through line 32.

bllizedt residual product which is substantially free Vfrom such undesired'gaseous constituents and which can therefore be fractionated effectively and rapidly in subsequent operating steps. The hydrocarbon mixture which is introduced to the stabilizer 26 is preferably preheated in exchanger 24 to a temperaturev in the range 250- 300 by heat exchange with the heavy pressure distillate or absorption oil, and rectification' thereof proceeds at the pressure indicated. In

in the line 38, or the absorber 34 may be elevated as shown, to obtain gravity flow into the column 26. The absorption oil is supplied to the absorber 34 at a rate and temperature which isl adapted to absorb substantially all of the desired hydrocarbons in the mixture removed from the stabilizer. Such desired hydrocarbons may include all Cs and higherhydrocarbons present in the vapor or gas stream entering the absorber The function of the absorberv 34 is, therefore, to recover these desired C3 and higherrhydrocarbons which would otherwise be lost, and to return such hydrocarbons to the stabilizing column 26, thereby recovering the maximum quantity of the desired Ca hydrocarbons. Unabsorbed'Cz hydrocarbons and gases reaching the top of absorber 34 are discharged from the system through a line 40 under the control of a relief vJalve 42.`

The mixture of hydrocarbons which collects at the bottom of the stabilizing column 26 as a result of the operations heretofore described should be substantially free of anyVV undesired C2 hydrocarboni or' lower molecular Weight constituents. The operating temperaturesfor the top and bot-- tom of the column are specifically designed\to effect this result. 1 The hydrocarbon mixture is withdrawn from the foot of the column 26 through a line 44, past a pressure relief v alve 44, and ls conducted to the first column 48 of a series of stabilizing and fractionating columns wherein the mixture may be fractionated to produce desired individual fractions, such as; forexample, a

' propane-propylene fraction,. a normal butane carrying 'out the fractionation'in column 26, the

bottom of the column is heated by means of a heater 28 to maintain the necessary temperature therein, as for example 375 F. At the same time the top of the `oolumri'26 is preferably cooled by means of a cooling coil 30 to produce a refluxing action. A

Under the specified pressure and temperature conditions for the loperation of the column 2 6 it i', practically impossible to make a clean separation between the C: and the Cn hydrocarbons. because at the high operating pressures specified the cooling and refluxing must be carried on by a mixture'of C; and Ca hydrocarbons foremcient reflux. Theloverhead vapor fraction which is produced by stabilizer 26 in accordance with e the/ present process comprises methane and the .Cz hydrocarbons ethaneand ethylene,` and also Y fraction, a butene-iso-butane fraction, a light gasoline fraction, and a heavy gasoline or higher boiling .distillate residue which may be recycled as an absorption oil to the absorbers I8 and 34. The stage fractionation to accomplish the desired result is greatly simplified and much more easily and economically effected because ofthe absence of all but possible traces of ethane, ethylene and v lower molecularcweight constituentsin the mate-- elivered tothe fractionating sysrial which is tem through t e line 44.

By reason of substantially vcomplet-Ae'removal of C1 and C2 hydrocarbons from the-richabsorption oil or distillate bottoms Jproduct of thestablizing operation in'tower 26, it is possible to treat -f tower 48 under condition such product to a second stabilizing operation in sofgreatly reduced pressure and heavy reflux adapted to fractionally dis- `the tower 48 -pass upwardly thr ugh filling of bubble trays therein countercurre lt to reflux condensate introduced by a reflux return line. 52.

Cahydrocarbon vapors leavingr the top of tower l48 pass by a line 54 into the midzone of a fractionating still 56 at a point `iust below a condensate trap plate 58. Column still 56 is oper- Y ated to remove the last trace of Cz hydrocarbon by venting at valve 66. The lower portion of still 56 is operated as a propane reboiler, while the upper portion' of the still is operated as a propane vapor condenser developing reflux for use in tower 48.

By reason of the lfact that the vapors entering still 56 are substantially free of C2 hydrocarbons,

it is possible to operate condenser 60 at the top/ of tower 56 to establish substantially equilibrium condensation, without overloading or fouling the condenser. The C3 hydrocarbons thus condensed in the upper portion of still 56 collect on tray 58 and part of this product is returned as reflux `to the tower 48 by a pump 82. Heat for the reboiling operation in the lower portion of still 56 is supplied by a coil heater 61. The puriiied C: hydrocarbon or propane fraction is removed from the base of the still 56 through a line 68 and a cooler 10, to storage. Any water vapor extracted by the hydrocarbon oil from. the gas passed through absorbers I 0 and 34 is driven off overhead along with the propane vapors from tower 48 and condenses in the upper part of st ill 56, where it is collected as a bottom layer under the reflux liquid on trap tray 58. This water is drawnoi s through a line 12 into an accumulator 14, from which it is removed.

The rich absorption oil 'or distillate which collects as a bottom product in the base of column 48 is removed through a line 16, past a pressure reducing valve 18, into the mid-zone of a third stabilizer or fractionating tower 80. Tower 80 is operated to remove C4 hydrocarbons from the absorber oil, including allbutenes, isobutane and any excess normal butane not necessary for the vapor requirements of the light gasoline which is to be subsequently extracted from the absorption oil. Heat required for liberating the C4 hydrocarbons from the absorption oil is supplied by the coils of a heater 82 located at the base of tower 80. The tower 80 is operated at a greatly reduced pressure and under reflux and temperature conditions adapted for effecting removal of predetermined proportions of the butane along with all of the isobutane and butene fractions.- Reflux for operating the tower is introduced intov the top of the tower through a line 84. The fractionated C4 hydrocarbon vapors leave the top of the tower 80 through line 86 and enter the midzone of a fractionating still 88 just belowa reflux trap 90. The reflux condensate which is incharged to the column. Heat for carrying out the fractionation and reboiling within tower 88 is supplied by a tubular heater 94 located lat the base of the tower. -Vapors of C4 hydrocarbons leave the top of tower 88 through a vapor line |02 and are condensed by a condenser |04. The condensate is collected in a receiver 96 from which reflux condensate is returned tothe top of tower 88 by a reflux return pump' 98 and reiiux return line |00. Any condensate not returned as reflux is passed to storage or further rening through a cooler |05 and a valved draw-oil? line |06. As previously indicated. this condensate includes 'the isobutane and butenes. The temperature of the condenser |04 is regulated by a thermostatic valve |08 which in turn controls the supply of cooling fluid to the condenser |04. The normal butane which collects at the bottom of tower 88 is withdrawn through a line ||0 and a cooler ||2 past a drawoi! valve ||4 to storage.

After being stripped of undesired gaseous hydrocarbons and desired light C3 and C4 hydrocarbons by the treatment in stabilizer columns 26, 48 and 80, the absorption oil or distillate is withdrawn from the bottom of tower through a line ||6, past a reducing valve ||8, into the midportion of a'nal fractionating still |20 which is preferably operated at substantially atmospheric pressure. Heat for the operation within still |20 is supplied by a coil heater |22, and the still is operated to distill off overhead all light gasoline hydrocarbons from the absorption oil-or heavy distillate preparatory to return of the absorption oil or distillate heavy gasoline as an absorption menstruum to the absorbers |0 and 84 for reuse therein. Fractional distillation is carried out within still |20 with the aid of reflux returned thereto from a light gasoline receiving tank |24 by a reflux return pump |26 and a return line |28. Light gasoline vapors leave the top of still |20 through a line |30 and are condensed by passing through a condenser |32, the condensate collecting in receiver |24. Stripped heavy gasoline or other absorber oil is removed from the base of the still |20 and may be passed through heat exchange coils in preheater 24 and in a cooler |34, on the way to the intake of a pump |36. Pump |36 is used to force the denuded absorber oil through lines .I8 and 36 to the primary and secondary absorbers.

Since the heavy gasoline which remains in the' bottom of still |20 is one of the products of the distillate operation, there is always some excess thereof produced ,over and above that amount which may be employed as absorber oil in cyclic circulation through the apparatus. Any excess heavy distillate not required as absorber oil is withdrawn to storage through valvedA line |38. 'I'his absorption oil may contain 'all hydrocarbon products oi' the process between the end 'boiling point oi the light gasoline taken oil overhead from still |20 and the end point of the heavy ends of the product entering the absorber 0, which troduced into the top of still 80 is a part of the condensate produced by condensing vapors in the upper portion of tower` 88 and in a vapor condensing and reflux return system operatively connected with the top of tower 88. The reflux thus produced in the top of tower 88 is returned to tower 80 by a reiiux return pump 92.

may be up to 650 F. The pump |36 of course operates to raise the pressure of the recycled absorption oil to a pressure corresponding to the operating pressure of the secondary absorber 34 Tower 88 is operated as a rectifying still to separate all of the butenes and isobutane from 1 the normal butane which is present in th 'vapors 'Il pressure for the primary absorber |0 is in (approximately .500 lbs.). For this reason a valve is provided in the inlet pipe I8 to absorber 0 since the operating pressure of this absorber is considerably lower than that of absorber 34. However, these oils may be delivered to each absorber by two separate pumps. y

.As previously indicated, the preferred operattem is operable without requiring the use of com- 10 'pressors for compressing gaseous hydrocarbons from a low pressure to a high pressure.v Even the undesired hydrocarbons whichare absorbed in the primary absorber have their pressure raised tothe pressure of subsequent stabilizing operations by means of the liquid pump 22.. All subsequent handing of uids in the process is effected without the use of compressors, either Iby carrying out the operation atia pressure below that of the preceding operation in the cycle, or by -using other liquid pumps such as the reflux return pumps 62.92, 98 and |28.

The invention having been thus described, what is claimed as new is: f

l. In vthe fractionation of hydrocarbon mixtures containing C3 and C4 hydrocarbons and hydrccarbons of gasoline boiling range in which the'fractionation is carried out vfor the purposeof producing Ca and C4 fractions which are substantially free of constituents of higher and lower\ molecular weight, the improvement' which comprises passing a hydrocarbon mixture to be iractlonatedcontaining C5, C4 and gasoline boiling Srange hydrocarbons whichA is substantially free of but contains traces of C; hydrocarbon into al fractionating column in which the mixture is subjected to rectification under controlled tern- -perature and pressure conditions adapted to produce a bottoms product `substantially free of Cz and'Ca hydrocarbons and overhead vapor fraction consisting essentially of C: and Cz hydrocarbons but which is substantially free of C4 hydrocarbon, introducing the'said vapor fractiondirectly into the midportion of a second fractionating column in vwhich the vapor mixture is rectiiied under wonditions adapted-to eliminate the C: hydrocarbon overhead, withdrawing a Ca -hydrocarbon condensate from 'said-second fractionating' .column at a point above the point of introduction of said vapor fraction and introduclng it into the top of said mst-mentioned fractlonating column to provide refluxtherefor, withmolecular weight, the improvement which comprises passing a hydrocarbonmixture to be frac- Y `tionated containing Cs, C4 and gasoline boiling range hydrocarbons which is substantially free of but contains traces of Cz hydrocarbon into a fractionating columnin which the mixture is subjected to rectiilcatlon under controlledtemperature and pressure conditions apted to produce a bottoms product substantially free of C2 and Ca hydrocarbons and an overhead vapor fraction consisting essentially of Cs and C: hydrocarbons .but which is substantially-free of C4 hydrocarbon, introducing the said vapor fraction directly into the midportion 'of a second fractionatlng column in,which the vapor mixtureis `rectiiled under conditionsl adapted to eliminate the Ca hydrocarbon overhead, withdrawing a liquid C3 hydrocarbon fraction from the bottom of said second column, passing the bottoms product from said first-mentioned, fractionating column which is substantially free of Cz and C3 hydrocarbons into a third fractionating column and therein rectifying the fsame under conditions adapted to remove overheadsl vapor fraction consisting essentially, of i C4 hydrocarbon, passing the C4 hydrocarbon vapor fraction into the midportion of a fourth fractionating column Iand therein rectifying the vapor mixture under conditionstadapted to produce an overhead C4 fraction which is substantially free of normal bu-` tane, withdrawing a condensate from said fourth fractionating column at a point above the point of introduction of said C4 hydrocarbonvapor fraction and introducing it into the upper portion ofdsaid third fractionating column to provide reflux therein. y

3. In the 'fractionation vof hydrocarbon mixtures containing C3 and C4 hydrocarbons and hy- Ydrocarbons of gasoline boilingrange in which the fractionation is carried out for the purpose of producing a Ca `fraction which is substantially free of constituentsof higher and lowermolecular weight, the improvement which comprises passing a hydrocarbon mixture to be fractionated containing Cz, C4 and gasoline boiling range hydrocarbons which is substantially free. of but drawing a substantially .pure Cs hydrocarbon liq-` 4.

uid fraction from the bottom of said second column, passing the bottoms product from said rstmentioned fractionating column consisting essentially of C4 and higher`molecular weight hydrocarbons'into a third fractionating column and therein rectifying the same under conditions adapted to remove overhead a vapor fraction conl"distingo e tion of'a fourth fractionating'rcolumn and therein rectifying the vapor mixture under conditions 'f adapted to produce an overhead C4 fraction which is substantially free of normal butane. Withdrawing a condensate from said fourthfractionating column at a point abovethe point of introduction or said C4 hydrocarbon vapor fraction and ntially of C4 hydrocarbon, passing the C4 hydr arbon vapor fraction into the mid-porw contains' traces of Cz hydrocarbon into a frac-- tionating column .in which the mixture is sub-I jected to rectification under controlled temperature and pressure conditions adapted to produce a bottoms product free of Cz and' Ca hydrocarbons and' an overhead vapor fraction consisting essentially of Ca hydrocarbon and some Cz hydrocarbon but which is free or` C4 -hydrocarbon, introducing the said vapor `fraction di-A rectly into the midportion of a second fraction` ation column in which thevapor mixture is rectitled under reuxing. conditions adapted to eliminate the C2 hydrocarbon overhead, with-I drawing a C: hydrocarbon condensate from said second fractionating column at a point above the introducingit into the upper portion of said 'w third fractionating column toy provide reflux therein. f y

-2. I n the fractionation of hydrocarbon mixtures containing C3 and C4 hydrocarbons and hydrocarbons o f gasoline boiling range inwhich point of introduction of said vapor fraction and introducing it into the top of said first-mentioned fractionating column to provide reflux therefor, discharging C; hydrocarbon from the /top of the second column, withdrawing a substantially pure C: hydrocarbon liquid fraction from the bottom of said second column, and withdrawing C4 and gasoline boiling range hydrocarbons from the bottom of the first. column for further fractionation of the heavier hydrocarbons.

' DAVlD G. BRANDT. 

